Dyeing and printing of cellulose esters and of linear aromatic polyesters with mono-sulfonated anthraquinones



United States Patent 2,843,448 DYEING AND PRINTING 0F CELLULOSE ESTERS AND OF LINEAR AROMATIC POLYESTERS WITH MONO-SULFONATED ANTHRAQUINONES Ludwig Thummel, Emil Metzger, and Jacques Guenthard, Basel, Switzerland, assignors, by mesne assignments, to Saul & Co., Newark, N. J., as nominee of Fidelity Union Trust Company, executive trustee under Sandoz Trust No Drawing. Application December 29, 1955 Serial No. 556,037 Claims priority, application Switzerland January 5, 1955 18 Claims. (Cl. 8-57) The present invention relates to the dyeing and printing of cellulose esters and of linear aromatic polyesters.

It is old to dye or to print articles (for example threads, fibers, bands, fabrics, sheets and the like) of cellulose esters and of linear aromatic polyesters with dispersion dyestuffs in the presence of swelling agents for the said esters and polyesters. However, these processes involving the use of dispersed dyestuffs are bound up with various deficiencies. For example, finely divided dyestufis, such as are employed for the preparation of printing pastes and dyeing and padding liquors, are prepared only with considerable difficulty. Moreover, it is difiicult to obtain uniform dyeings of wound articles (e. g. skeins or balls of yarn, etc.) in a circulating liquor with the aid of dispersed dyes, since the wound articles exert a filtering action on the liquor. In addition to the known dyeing and printing processes for cellulose esters by means of dispersed dyes, printing processes for these esters by means of water-soluble dyestuffs are also known. However, dyeing obtained according to these last-named processes generally have only a fair fastness to light in addition to an unsatisfactory fastness to washing; many of them have a poor fastness to light. It is a desideratum in the art, therefore, to develop a simple process for the dyeing and printing of cellulose esters and linear aromatic polyesters with water-soluble dyestuffs, which process is free of the afore-enumerated deficiencies. A primary object of this invention is the embodiment of such a process.

The said object is achieved by the present invention which makes it possible to dye and to print articles of cellulose esters and of linear aromatic polyesters in level (uniform), light-fast and wash-fast shades by the action of water-soluble dyestuffs, as hereinafter defined and which contain a single sulfonic acid group in the molecule thereof, on the said articles in the presence of a reducing agent and, if necessary, in the presence of a swelling agent for the ester or polyester. It is found that, when following this procedure, the dyestuffs drawn onto the material being dyed or printed are free of sulfonic acid groups. In other words, in the dyeing liquor or in the printing paste, the dyestulf splits ofi its sulfonic acid group by the action of the reducing agent in the heat, is thus converted into water-insoluble form, and draws onto the material in a state of molecular subdivision.

The process of the invention may be characterized as a process for the dyeing and printing of articles of cellulose esters and of linear aromatic polyesters with watersoluble dyestuffs from aqueous dye-baths at elevated temperatureor with the aid of aqueous printing pastes' and padding liquors, followed by steaming of the prints and pa-ddings, if necessary with the use of pressure. The water-soluble dyestuffs employed in practicing the pres- 2,843,448 Patented July 15, 1958 printing or padding is, according to the invention, carried out in the presence of a reducing agent and, if necessary, in the presence of a swelling agent for the cellulose ester or for the linear aromatic polyester being treated.

The invention further relates to dye-baths, printing pastes and padding liquors which are suitable for use in the process, according to this invention, for the dyeing and printing of articles of cellulose esters and of linear aromatic polyesters. They are characterized by their content of one or more dyestuffs of the type defined in the preceding paragraph, of a reducing agent, and if desired, of a swelling agent for the cellulose ester or for the linear polyester to be treated.

The term cellulose esters, as herein employed, refers primarily to dicellulosepentaacetate (acetate silk) and cellulose triacetate, and the term linear aromatic polyesters refers to high molecular products from polyalkyleneglycols and aromatic dicarboxylic acids, such for example as those which are commercially available as Dacron or Terylene. Dacron is a synthetic fiber made by the condensation of dimethyl terephthalate and ethylene glycol. the polyethylene terephthalate type.

Dacron tively for their polyethylene terephthalate fibers.

The process of the invention can be carried out in: Thus, the dyeing of cellulose ester can:

diverse ways. be carried out in the absence of swelling agents at C. for acetate silk and at C. for cellulose triace-- tate, while the dyeing of linear aromatic polyester at:v

the boiling point of water requires the presence of a swelling agent for the polyester. Swelling agents which are suitable for use according to the invention comprise, for example, tetraline, trich-lorobenzene, benzoic acid, 2-hydroxy- 1 1 -diphenyl, 4-hydroxy- 1, 1'-diphenyl, The dyeing of the linear aromatic polyester can also be carried out at elevated temperature, e. g. at C. and

under pressure, for example in a conventional high tem- The articles of cellulose esters and of linear aromatic polyesters, dyed or printed according to the present invention, are characterized by good dye penetration, i. e. the material is dyed all the way through, and this is the case especially with thick fabrics and wound articles (skeins and the like). The prints and dyeings are of very good uniformity, i. e. they are level, and they are also fast to light and to washing.

Preferred reducing agents for the purposes of the present invention are zinc-formaldehyde-sulfoxylate, sodiumformaldehyde-sulfoxylate and sodium-formaldehyde-bisulfite, the first of these being advantageously employed when dyeing from an aqueous bath; sugar in alkaline medium, for example, glucose, galactose, fructose, lactose; sodium-cellulose-xanthate. Other reducing agents such, for example, as alkali metal hydrosulfite, stannous give rise to by-products.

ent invention are acid dyestuffs of the anthraquinone series which contain in the 2-position of the anthraquinone nucleus, as the sole water solubilizing group, a sulfonic acid group which splits off by the action of a reducing agent at elevated temperature. The dyeing,

The water-soluble, acid dyestuifs of the anthraquinone series, which are employed according to the present invention, must fulfil the previously-mentioned requirements that they contain in the 2-position of the anthraquinone nucleus a sulfonic acid group which splits off by the action of a reducing agent, and that for the rest Terylene is a synthetic fiber also of and? Terylene are trademarks of DuPont and ICI respec-- etc. 7

they are free of other water-solubilizing groups, and in particular that they are free of additional sulfonic acid groups orcarboxy groups; Such dyestuffs belong to the most'diverse classes of the anthraquinone series; thus,

in the course of 20 minutes, and is maintained at this temperature for 60 minutes. The dyed acetate silk is then withdrawn from thebath; rinsed and dried. It is dyed a level, pure violet shade of good fastness to light use may be made of for example salts of 1,4-diaminoand to washing. anthraquinone-Z-sulfonic acid, 1-amino-4-hydroxyanthra- Example 4 quinone'z'sulfonlc 9 1'ammo'4'phnylammoanthra' 100 parts of cellulose triacetate are introduced at q i acld p i' about 60 into a dye-bath which contains 3000 parts of ylammoanthraqumone-2-sulfome ac1d, 4,4 -d1am1no-1,1- Water, 2 parts of lithium 1 amino 4 n pentylsulfonyl dlanthrtm lde'z'sulfomc t 3 9 't j aminoanthraqninone-Z-sulfonate and 1.5 parts of zincpropylamm'la2"anthraPYr1d1ne'2's1tn.1 acld 3 formaldehyde-sulfoxylate. The dye-bath is heated to l q 4 fmethqxy) Bheflylammo anthra' 100 in the course of minutes, and is maintained at pyl'ldme'zjsulfomc' ac1d, this temperature for 60 minutes. The dyed cellulose triphenylammt"119'?HthTaPYQdme'Z'SUIfQmC f" 15 acetate is then removed from the bath, rinsed with water '1"" P Sulfonylammcanthraqumone 2 Sulfomc and dried. There is obtained a level, bright bluish red acld: dyeing of good fastness to water and to washing.

The; following examples set forth preferred representative illustrative embodiments of the invention. In these Example 5 6XaII 1P1@$ the PartS t y Weight, and the p P0 100 parts of polyester fiber are introduced at 60 into are 11; gr fg f when tt'te term Polyester a dye bath consistingof 3000 parts of water, 2 parts of fiber 1S employfid, this slgnlfiw that elther Dacron fibers sodium 1-amino-4-phenylarninoanthraquinone-Z-sulfonate, Telylfine'fibets y be used- 1.5 partsof 2-hydroXy-l,1'-diphenyl, 1.5 parts of aqueous Example 1 sodium hydroxide solution of 30% concentration by i V o weight, and 2 parts of fructose, whereupon the bath is 100 Parts of p'olfister fioer are Introduced at 60 h'eaftedn'to the boiling temperature in the course of 20 at dye-bathfonslstllng of (20 Parts of Water Pans of minutes. The material being dyed is maintained in the Sodium; 3 'carbetnOXY'4"(2 P bathtor 60 minutes at 100, then withdrawn from the thrapyridine-Z-sulfonate, 1.5 parts of zmc-formaldehydedyesathj Washed with Water and dried The polyflter stltfoxylate and Parts of f fiber is dyed a blue shade of good fastness to washing. whereupon the bath is heated to boiling in the course of 30 20 minutes. The material being dyed is maintained in Example 6 the bath for 60 minutes at this temperature, and is then 103 pal-ts f acetate ilk. are i nd d at about 60 withdrawn from the bath, rinsed with water and dried. i aqgdwyebath consisting. f 3 parts f water, 2 parts. The: polyester fiber 1s dyed a level yellow shade of good f Sodium 1 i 4 4'- i h l m i. fastmss 0 e and t0 Washlngnone Z-sulfonate, 2 parts of glucose and 2 parts of so- Example 2 diuin carbonate. The dye-bath is heated to 80 in the r I I eourse'of 20 minutes. After minutes at the'dyed 1J0 P t of Pmyestar fiber are dyed m a high tempera" acetate silk is withdrawn from the bath, rinsed anddried. ture dyeing apparatus under pressure at a temperature It is dyed a level greenish blue Shade of good, fastness to above for a period of 30 minutes with a dyemg 40 washing llquor,which ,(ienststs of ,3000 patts of 4 parts of The following table exemplifies additional embodiments M351um 1'tlydrox30413116131ammoanmlaqumoilez'sul' of the invention. The fiber being treated is set forth fonate and 1.5 parts of zmc-formaldehyde-suhoxylate. in thesecond column the,dyestufi employed is recited A t the end of this time, the polyester fiber 1s dyed a level 1 in the third column, the reducingagent used is indicated violet shade of good fastness to light and to washing. 4.) in the fourth column, and the C0101. of the obtaineddyb Example 3 ing is shown in the last column. Where the fiber is a r I O polyester fiber, the procedure-followed is that of any one 100 parts of acetate silk are introduced at about 60 of Examples 1 2 and 5- Where the fiber is anetate silk V a dye'bath Winch ccllslsts of 3000 Parts of Water, y the procedure followed is that of either one of Examples P t Of ammfmlum y y- Y)"p y 3 and6; Example 14'follows the procedure according ammoanthraqumone-2-sulfonate and 1.5 parts of ZinC- to Example 4. In every' case, a l l dyeing f gocd formaldehyde-sulfoxylate. The dye-bath is heated to 80 fastness properties'is obtained:

Exlzmple Fiber Product Reducing Agent Color 7 polyester sodium 3-earbethoxyzinc-formaldehydeorange.

4 phenylamino 1,9 sulioxylate.

anthra-pyridine-Z-suitomato. 8 do sodium 1-hydroxy-4-cydo red-violet.

anamylaminoanthraquinone-Z-sulfonate. 9 do sodium 1,4-di-p-(mcthgalactose green.

oxy) ethoxyethoxy antlino anthraqui none-2-su1fonate. 10 do sodium4,4-diamino-1,1- glucose gray.

di-anthrimide-2-sulfonate. 11 acetate si1k. sodium 1-amino-4-hyzinc-formaldehydered,

droxy-anthraquinoneulfoxylate. 2-sulfonate. 12 do sodium l-aminoA-phenyldo blue.

aminoanthraquinone 2-sulfonate. 13 do sodium 1-amino-4-hysodium-celluloscred.

droxyanthraquinone xanthate. Z-SlllfOllfltG. l4.. cellulose ,trisodium 1 -amino-4- (4-hyzine-formaldehydeblue. acetate. droz'r'y) -phenylaminosulfoxylate.

. anthraqUlnone-Z-sulinnate:

Example A spool of 100 parts of polyester fiber is dyed in a high temperature dyeing apparatus as follows: a dyeliquor of 4 parts of sodium 3'-carbethoxy-4-(4'-chloro)- phenylamino-1,9-anthrapyridine-Z-sulfonate, 1.5 parts of zinc-formaldehyde-sulfoxylate and 4000 parts of water is circulated in the apparatus, and is quickly brought to boiling temperature. The temperature is then raised so that in the course of 60 minutes 125 has been attained. At 1 the end of this time, the spool is dyed a level orange shade which is fast to light and to washing.

Example 16 A fabric of polyester fiber is printed with a printin 15 paste of the following composition: I

20 parts of potassium 3'-carbethoxy-4-(2'-cyano)-propylamino-l,9-anthrapyridine-Z-sulfonate 100 parts of thiodiglycol 20 450 parts of gum thickener 20 parts of sodium-formaldehyde-sulfoxylate 20 parts of potassium carbonate 390 parts of water 1000 parts The print is dried at 50, then steamed for minutes at normal pressure (temperature 100-105) and for 10 min- 30 utes at a pressure of 1.8 atmospheres (temperature 120), then rinsed with cold water, soaped at 50 with a fatty alcohol sulfonate, again rinsed and finally dried. There is obtained a level yellow print of good fastness to light and to washing.

Example 17 10 parts of sodium 1-amino-4 phenylaminoanthraquinone-Z-sulfonate 100 parts of thiodiglycol 450 parts of gum thickener 80 parts of sodium-formaldehyde-bisulfite 20 parts of potassium carbonate 340 parts of water 1000 parts are worked up into the form of a printing paste. A fabric of polyester fiber is printed with the thus-prepared paste. further treatment is as described in Example 16. There is obtained a bright blue level print of good fastness to light and to washing.

Example 18 A fabric of polyester fiber is padded on the foulard with a padding liquor of the following composition:

1000 parts The padding is steamed and finished after the manner described in Example 16. There is obtained a level violet dyeing of good fastness to light and to washing.

Example 19 A fabric of polyester fiber is padded after the manner 6 set forth in Example 18 with a padding liquor of the following composition:

20 parts of potassium 3-carbethoxy 4 (4-chloro)- phenylamino-1,9-anthrapyiidine-2-sulfonate 100 parts of thiodiglycol 200 parts of gum thickener parts of sodiumeformaldehyde-bisulfite 20 parts of potassium carbonate 580 parts of water 1000 parts The padding is treated after the manner described in Example 16. There is obtained a level orange dyeing of good fastness to light and to washing.

In the examples which follow, printing paste ingredients are set forth. These are used, in printing paste form, for the printing of the enumerated fabrics. In each case, the fabric is dried after being printed. In the case of acetate silk fabrics, the print is then steamed for 30 minutes at 103 at atmospheric pressure. In the case of fabrics from cellulose triacetate and for polyester fiber, the print is steamed for 30 minutes at 102 104 at atmospheric pressure and for 15 minutes at 112 at a pressure of about 1.5 atmospheres. After steaming, the print is in each case rinsed with water, soaped for 3 minutes at 60, again rinsed and finally dried.

Example 20 20 parts of sodium 3' carbethoxy 4 mesidino 1,9-

anthrapyridine-2-sulfonate 100 parts of thiodiglycol 330 parts of water 450 parts of gum thickener 50 parts of potassium carbonate 50 parts of sodium-formaldehyde-sulfoxylate 1000 parts Print on polyester fiber: orange.

Example 21 20 parts of sodium 1-amino-4-isopentylsulfonylaminoanthraquinone-Z-sulfonate 100 parts of thiodiglycol 375 parts of water 450 parts of gum thickener 50 parts of potassium carbonate 5 parts of galactose 1000 parts Print on polyester fiber: bluish red.

Example 22 20 parts of sodium 1 amino 4 p anisidinoanthraquinone-Z-snlfonate 100 parts of thiodiglycol 340 parts of water 450 parts of gum thickener 50 parts of potassium carbonate 40 parts of lactose 1000 parts Print on polyester fiber: blue.

Example 23 7 8 Example 24 Example 30 20 parts of sodium et,4'-diamino-l,l'-dianthrimide 2- 20 parts of sodium 1-hydroxy- 4.-(pmethoxy.)-phenylsulfonate aminoanthraquinone-Z-sulfonate 100 parts of thiodiglycol 5 100 parts of thiodiglycol 260 parts of water 360 parts of water 450 parts of gum thickener 4570 parts of gum thickener 50 parts of potassium carbonate 50 parts of potassium carbonate 120 parts of dextrine V 20 parts of glucose 1000 parts 1000 parts Print on polyester fiber: gray. Print on cellulose triacetate: violet. V Example 25 Example 3] 20 parts of sodium 1-amino-4-hydroxyanthraquinoneparts of sodium 1-an1ino-4-(p-Inethoxy)phenyl- Z-SUIfOBate aminoanthraquinone-2-sulfonate 00 parts of Tetracarnit 80 parts of thiodiglycol 375 Parts of Water 20 .parts of Tetracarnit 450 parts of gum thickener 3 0 parts f Water 50 parts of potassium carbonate 20 450 parts f gum hi k 5 parts of Hydrosulfit conc. (sodium hyposulfite) 50 parts of potassium carbonate 20 partsof sodium hyposulfite 1000 parts Print on polyester fiber: red. 1000 Parts E l 26 Y Print on cellulose triacetate: blue.

20 parts of sodium l-hydroxy-4-phenylam'inoanthra- In the foregoing examples Where gum thickener is used,

quinone-Z-sulfonatc i m y b g ab e, m t ag c th n a e ll,

80 parts of thiodiglycol crystal gum.

20 parts of Tetracarnit 3 Tetracarnit is an agent for dissolving dyestulfs and 370 parts of Water for levelling on the basis of heterocyclic bases. Tetra- 450 parts of gum thickener earnit is a trademark of Sandoz.

30 parts of potassium carbonate ,Having thus disclosed the invention, what is claimed is:

30 parts of zinc dust v '35 l. A process for dyeing and printing articles of cellulose esters and of linear aromatic polyesters, which com- 1000 parts prises bringing said articles into contact with a Watersoluble acid anthraquinone dyestuif containinga sulfouic P t l este fib r: violet.

mm on p0 y r e ac1d group In the 2-pos1t1on of the anthraqu none nucleus Example 27 40 as the sole water-solubilizing group, in aqueous medium 20 parts of sodium l-aminoanthraquinone-Z-sulfonate and at raised temperature and in the Presence of a 109 parts of hi di l l ducing agent selected from the group consisting of zinc- 360 Pal-ts f Water formaldehyde-sulfoxylate, sodium-formadlehyde-bisulfite, 450 parts of gum thi kene sodium-formaldehyde-sulfoxylate, sodium-cellulose-xan- 56 parts f potassium rb at thate, a mixture of sodium hyposulfite and an alkali 20 art of sodium-formaldehydosulfoxylate metal carbonate, a mixture of a reducing sugar andan alkali metal carbonate, a mixture of a reducing sugar 1000 parts and an alkali metal hydroxide and a mixture of Zinc dust and an alkali metal carbonate, whereby the 2-posi- Punt on acetate $11k: Orange tioned sulfonicacid group is split ofif and the dyestuff is Example 2 drawn onto the said articles in insolubilized form and .in a state of molecular subdivision. 20 Parts Of Sodlum 1ammo-4'phenylamlnoallthfaqm' 2. A process according to claim 1, wherein the reducnone-2-s ulfen t ing agent is zinc-formaldehyde-sulfoxylate. 100 Parts of thlodlglycol 3. A process according to claim 1, wherein the reduc- 320 Pillts of Water ing agent is areducing sugar. 450 Parts Of u thlckenel' 4. A process according to claim 1, wherein the reduc- 50 parts of potassium carbonate i agent i glucose,

Parts of fructose 5. A process according to claim 1, wherein acetate silk 60 is dyed from an aqueous dye-bath at a temperature of 1000 parts about 80 C.

Print on acetate silk: b1ue 6. A process according to claim 1, wherein cellulose triacetate is dyed from an aqueous dye-bath at a tem- Example 9 perature of about 100 C.

7. A process according to claim 1, wherein av linear aromatic polyester material is dyed at a temperature of about 100 C. in the presence of a swelling agent for the said polyester material.

8. A process according to claim 1 wherein the said dyestulf is comprised within an aqueous printing paste which also comprises said reducing agent, said paste is 20 parts of sodlumformaldehydersulfoxylate printed onto the material being treated and the thusobtained print is steamed. 1000 parts 9. A process according to claim 8, wherein said re- Print on cellulose triacetate: orange. ducing agent is sodium-formaldehyde-sulfoxylate.

20 parts of sodium 3'-carbethoxy-4-(p-methoxy)-phenylamino-1,9-anthrapyridine-2-sulfonate parts of thiodiglycol 360 parts of water 450 parts of gum thickener 50 parts of potassium carbonate 10. A process according to claim 8, wherein said reducing agent is a reducing sugar.

11. A process according to claim 8, wherein said reducing agent is glucose.

12. A process according to claim 1 wherein said dyestuff is comprised within a padding liquor which also comprises said reducing agent, said padding liquor is applied to the material being treated and the thus-obtained print is steamed.

13. A process according to claim 12, wherein said reducing agent is sodium-formaldehyde-sulfoxylate.

14. A process according to claim 12, wherein said reducing agent is a reducing sugar.

15. A process according to claim 12, wherein said reducing agent is glucose.

16. A process according to claim 8, wherein said material is acetate silk and the print is steamed at about 100 C.

1O 17. A process according to claim 8, wherein said material is cellulose triacetate and the print .is steamed at above 100 C.

18. A process according to claim 8, wherein said material is a linear aromatic polyester and the print is steamed at above 100 C.

References Cited in the file of this patent UNITED STATES PATENTS 1,833,250 Grossmann Nov. 24, 1931 1,904,815 Bally Apr. 28, 1933 FOREIGN PATENTS 358,033 Great Britain Sept. 28, 1931 965,896 France Feb. 22, 1950 

1. A PROCESS FOR DYEING AND PRINTING ARTICLES OF CELLULOSE ESTERS AND OF LINEAR AROMATIC POLYESTERS, WHICH COMPRISES BRINGING SAID ARTICLES INTO CONTACT WITH A WATERSOLUBLE ACID ANTHRAQUINONE DYESTUFF CONTAINING A SULFONIC ACID GROUP IN THE 2-POSITION OF THE ANTHRAQUINONE NUCLEUS AS THE SOLE WATER-SOLUBILIZING GROUP, IN AQUEOUS MEDIUM AND AT RAISED TEMPERATURE AND IN THE PRESENCE OF A REDUCING AGENT SELECTED FROM THE GROUP CONSISTING OF ZINCFORMALDEHYDE-SULFOXYLATE, SODIUM-FORMADLEHYDE-BISULFITE, SODIUM-FORMALDEHYDE-SULFOXYLATE, SODIUM-CELLULOSE-XANTHATE, A MIXTURE OF SODIUM HYPOSULFITE AND AN ALKALI METAL CARBONATE, A MIXTURE OF A REDUCING SUGAR AND AN ALKALI METAL CARBONATE, A MIXTURE OF A REDUCING SUGAR AND AN ALKALI METAL HYDROXIDE AND A MIXTURE OF ZINC DUCT AND AN ALKALI METAL CARBONATE, WHEREBY THE 2-POSITIONED SULFONIC ACID GROUP IS SPLIT OFF AND THE DYESTUFF IS DRAWN ONTO THE SAID ARTICLES IN INSOLUBILIZED FORM AND IN A STATE OF MOLECULAR SUBDIVISION. 